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At least 1,117 records · Page 62

Remote chirality transfer in low-dimensional hybrid metal halide semiconductors

In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (g CD ) of up to 10-2. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. Additionally, this concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality.

14 SOLAR ENERGY↗

Probing high-momentum protons and neutrons in neutron-rich nuclei

The atomic nucleus is one of the densest and most complex quantum-mechanical systems in nature. Nuclei account for nearly all the mass of the visible Universe. The properties of individual nucleons (protons and neutrons) in nuclei can be probed by scattering a high-energy particle from the nucleus and detecting this particle after it scatters, often also detecting an additional knocked-out proton. Analysis of electron- and proton-scattering experiments suggests that some nucleons in nuclei form close-proximity neutron–proton pairs with high nucleon momentum, greater than the nuclear Fermi momentum. However, how excess neutrons in neutron-rich nuclei form such close-proximity pairs remains unclear. In this study we measure protons and, for the first time, neutrons knocked out of medium-to-heavy nuclei by high-energy electrons and show that the fraction of high-momentum protons increases markedly with the neutron excess in the nucleus, whereas the fraction of high-momentum neutrons decreases slightly. This effect is surprising because in the classical nuclear shell model, protons and neutrons obey Fermi statistics, have little correlation and mostly fill independent energy shells. These high-momentum nucleons in neutron-rich nuclei are important for understanding nuclear parton distribution functions (the partial momentum distribution of the constituents of the nucleon) and changes in the quark distributions of nucleons bound in nuclei (the EMC effect). They are also relevant for the interpretation of neutrino-oscillation measurements and understanding of neutron-rich systems such as neutron stars.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Basin-scale study of CO 2 storage in stacked sequence of geological formations

Commercial scale decarbonization through carbon capture and storage may likely involve many CO 2 storage projects located in close proximity. The close proximity could raise concerns over caprock integrity associated with reservoir pressure buildup and interference among adjacent projects. Commercial-scale injection will also require large prospective CO 2 storage resource and high injectivity in the targeted storage formations. To accommodate the need for both large resource and high injectivity, project operators could consider injecting CO 2 into a stacked sequence of formations. This analysis investigates the benefits of injecting CO 2 into a vertically stacked sequence of saline formations, over injecting the same amount of CO 2 into a single saline formation, in addressing these challenges. Our analysis shows that injecting into the stacked sequence mitigates the extent of pressure buildup among the stacked formations, while still achieving the same or greater target CO 2 storage volumes. Among cases modeled, the resulting pressure buildup front is most reduced when each storage site distributes injection volumes over several wells, each of which injects a portion of the total CO 2 mass across the stacked sequence. This favorable case not only results in the smallest CO 2 aerial footprint, but also shows the largest reduction in the pressure buildup at the top of perforation at the injection wells (upwards of approximately 46% compared to the single-formation storage), the result of which is crucial to maintain caprock integrity. This analysis provides insights into required decision-making when considering multi-project deployment in a shared basin.

42 ENGINEERING↗

Amyloid structure exhibits polymorphism on multiple length scales in human brain tissue

Although aggregation of Aβ amyloid fibrils into plaques in the brain is a hallmark of Alzheimer's Disease (AD), the correlation between amyloid burden and severity of symptoms is weak. One possible reason is that amyloid fibrils are structurally polymorphic and different polymorphs may contribute differentially to disease. However, the occurrence and distribution of amyloid polymorphisms in human brain is poorly documented. Here we seek to fill this knowledge gap by using X-ray microdiffraction of histological sections of human tissue to map the abundance, orientation and structural heterogeneities of amyloid within individual plaques; among proximal plaques and in subjects with distinct clinical histories. A 5 µ x-ray beam was used to generate diffraction data with each pattern arising from a scattering volume of only ~ 450 µ3 , making possible collection of dozens to hundreds of diffraction patterns from a single amyloid plaque. X-ray scattering from these samples exhibited all the properties expected for scattering from amyloid. Amyloid distribution was mapped using the intensity of its signature 4.7 Å reflection which also provided information on the orientation of amyloid fibrils across plaques. Margins of plaques exhibited a greater degree of orientation than cores and orientation around blood vessels frequently appeared tangential. Variation in the structure of Aβ fibrils is reflected in the shape of the 4.7 Å peak which usually appears as a doublet. Variations in this peak correspond to differences between the structure of amyloid within cores of plaques and at their periphery. Examination of tissue from a mismatch case - an individual with high plaque burden but no overt signs of dementia at time of death - revealed a diversity of structure and spatial distribution of amyloid that is distinct from typical AD cases. As a result, we demonstrate the existence of structural polymorphisms among amyloid within and among plaques of a single individual and suggest the existence of distinct differences in the organization of amyloid in subjects with different clinical presentations.

59 BASIC BIOLOGICAL SCIENCES↗

Triplet–charge annihilation versus triplet–triplet annihilation in organic semiconductors

A triplet can annihilate with a charge or a triplet, generating triplet-charge annihilation (TCA) or triplet-triplet annihilation (TTA) in organic semiconductors. On one hand, the TCA and TTA are critical issues to improve optoelectronic responses by using triplet states. On the other hand, the TCA and TTA are important spin-dependent processes to generate magneto-optoelectronic responses. Our experimental studies find that the TCA is a dominant process over TTA in organic semiconductors. Specifically, we separately confine triplets with charges or with triplets towards the generation of TCA and TTA by adjusting triplet density, charge confinement, and charge/exciton ratio based on organic light-emitting diodes. We then use magnetic field effects of electroluminescence (MFEEL), as an experimental tool, to study the generation of TCA and TTA. We observe that the electroluminescence can show negative response to applied magnetic field, generating a negative MFEEL, when triplets and charges are simultaneously confined within close proximity by using interfacial confinement with unbalanced charge/exciton ratio. On contrast, the electroluminescence only exhibits a positive MFEEL when triplets are confined within close proximity by using interfacial confinement without unbalanced charge/exciton ratio. Therefore, it can be concluded from our MFEEL results that the TCA is a major process to annihilate triplets over than TTA. Clearly, this experimental finding provides a new understanding on controlling triplets-related optoelectronic and magneto-optoelectronic processes in organic semiconductors.

organic semiconductors↗

New coordination features; A bridging pyridine and the forced shortest non-covalent distance between two CO 3 2- species

The aerobic reaction of the multidentate ligand 2,6-bis-(3-oxo-3-(2-hydroxyphenyl)-propionyl)-pyridine, H 4 L, with Co (II) salts in strong basic conditions produces the clusters [Co 4 (L) 2 (OH)(py) 7 ]NO 3 (1) and [Co 8 Na 4 (L) 4 (OH) 2 (CO 3 ) 2 (py) 10 ](BF 4 ) 2 (2). Analysis of their structure unveils unusual coordination features including a very rare bridging pyridine ligand or two trapped carbonate anions within one coordination cage, forced to stay at an extremely close distance (d O···O = 1.946 Å). This unprecedented non-bonding proximity represents a meeting point between long covalent interactions and “intermolecular” contacts. Furthermore, these original motifs have been analysed here through DFT calculations, which have yielded interaction energies and the reduced repulsion energy experimented by both CO 3 2- anions when located in close proximity inside the coordination cage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient dual acidic carbo-catalyst for one-pot conversion of carbohydrates to levulinic acid

Levulinic acid (LA) is an important platform intermediate for several high value renewable bioproducts. One-pot synthesis of LA from carbohydrates is disadvantaged by the lack of proximity of the active sites required for sequential isomerization, dehydration and rehydration reactions. Herein, we report an efficient one-pot conversion of C 6 sugars to LA using a carbo-catalyst (ZrHyC), containing Lewis acidic zirconium and Brønsted acidic carboxyl and hydroxyl sites. The proximity of the two acid sites on a hydrothermally prepared carbon support makes the catalyst highly effective enabling a maximum 73% LA yield from glucose conversion. Fructose conversion achieved a higher LA yield (89%) because of a facile reaction without involving an isomerization step. The effects of solvents, the glucose to catalyst ratio, and the reaction time on glucose conversion and LA yield are systemically examined. Detailed characterization of the catalyst using FTIR, Raman spectroscopy, XPS, XRD, FESEM and NH 3 -TPD techniques are presented to elucidate the presence of the two acid sites and zirconium in the +4 oxidation state.

09 BIOMASS FUELS↗

$t_1$-Noise eliminated dipolar heteronuclear multiple-quantum coherence solid-state NMR spectroscopy

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe chemical and spatial proximities between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1 H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1 H detected D-HMQC solid-state NMR experiments is the presence of t 1 -noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t 1 -noise eliminated (TONE) D-HMQC, that minimize t 1 -noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t 1 -noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1 H π-pulses to refocus the evolution of 1 H CSA across each SR4 2 1 recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1 H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations at the end of each recoupling block, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire 1 H detected 2D 1 H{ 35 Cl} and 1 H{ 13 C} HETCOR spectra of histidine·HCl·H 2 O with reduced t 1 -noise. To show generality, we also apply these methods to obtain 2D 1 H{ 17 O} spectra of 20%- 17 O fmoc-alanine and for the first time at natural abundance, 2D 1 H{ 25 Mg} HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1 H– 25 Mg and 1 H– 27 Al proximities in Mg–Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated in situ spectroscopic studies on syngas production from partial oxidation of methane catalyzed by atomically dispersed rhodium cations on ceria

Catalytic reforming of methane to produce syngas is an important strategy for producing value-added chemicals. The conventional reforming catalyst relies on supported nickel nanoparticles. Here, in this work, we investigated singly dispersed Rh cations anchored on a CeO 2 catalyst (Rh 1 /CeO 2 ) for high activity and selectivity towards the production of syngas via partial oxidation of methane (POM) in the temperature range of 600–700 °C. The yields of H 2 and CO at 700 °C are 83% and 91%, respectively. The anchored Rh 1 atoms on CeO 2 of Rh 1 /CeO 2 are in the cationic state, and on an average each Rh 1 atom coordinates with 4–5 surface lattice oxygen atoms of CeO 2 . Compared to inert CeO 2 for POM, via the incorporation of single-atom sites, Rh 1 modifies the electronic state of oxygen atoms proximal to the Rh 1 atoms and thus triggers the catalytic activity of CeO 2 . The high activity of single-atom catalyst Rh 1 /CeO 2 suggests that the incorporation of single atoms of transition metals to the surface of a reducible oxide can modulate the electronic state of proximal anions of the oxide support toward forming an electronic state favorable for the selective formation of ideal products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unprecedented study of the broadband emission of Mrk 421 during flaring activity in March 2010

Because of its proximity, Mrk 421 is one of the best sources on which to study the nature of BL Lac objects. Its proximity allows us to characterize its broadband spectral energy distribution (SED). Here, the goal is to better understand the mechanisms responsible for the broadband emission and the temporal evolution of Mrk 421. These mechanisms may also apply to more distant blazars that cannot be studied with the same level of detail. A flare occurring in March 2010 was observed for 13 consecutive days (from MJD 55 265 to MJD 55 277) with unprecedented wavelength coverage from radio to very high energy (VHE; E> 100 GeV) γ-rays with MAGIC, VERITAS, Whipple , Fermi -LAT, MAXI, RXTE, Swift , GASP-WEBT, and several optical and radio telescopes. We modeled the day-scale SEDs with one-zone and two-zone synchrotron self-Compton (SSC) models, investigated the physical parameters, and evaluated whether the observed broadband SED variability can be associated with variations in the relativistic particle population. As a result, the activity of Mrk 421 initially was high and then slowly decreased during the 13-day period. The flux variability was remarkable at the X-ray and VHE bands, but it was minor or not significant at the other bands. The variability in optical polarization was also minor. These observations revealed an almost linear correlation between the X-ray flux at the 2–10 keV band and the VHE γ-ray flux above 200 GeV, consistent with the γ-rays being produced by inverse-Compton scattering in the Klein-Nishina regime in the framework of SSC models. The one-zone SSC model can describe the SED of each day for the 13 consecutive days reasonably well, which once more shows the success of this standard theoretical scenario to describe the SEDs of VHE BL Lacs such as Mrk 421. This flaring activity is also very well described by a two-zone SSC model, where one zone is responsible for the quiescent emission, while the other smaller zone, which is spatially separated from the first, contributes to the daily variable emission occurring at X-rays and VHE γ-rays. The second blob is assumed to have a smaller volume and a narrow electron energy distribution with 3 × 104<γ< 6 × 105, where γ is the Lorentz factor of the electrons. Such a two-zone scenario would naturally lead to the correlated variability at the X-ray and VHE bands without variability at the optical/UV band, as well as to shorter timescales for the variability at the X-ray and VHE bands with respect to the variability at the other bands. In conclusion, both the one-zone and the two-zone SSC models can describe the daily SEDs via the variation of only four or five model parameters, under the hypothesis that the variability is associated mostly with the underlying particle population. This shows that the particle acceleration and cooling mechanism that produces the radiating particles might be the main mechanism responsible for the broadband SED variations during the flaring episodes in blazars. The two-zone SSC model provides a better agreement with the observed SED at the narrow peaks of the low- and high-energy bumps during the highest activity, although the reported one-zone SSC model could be further improved by varying the parameters related to the emitting region itself (δ, B and R), in addition to the parameters related to the particle population.

79 ASTRONOMY AND ASTROPHYSICS↗

Hydropower Potential at Non-Powered Dams: A Multi-Criteria Decision Analysis Tool based on Grid, Community, Industry, and Environmental Impacts

Non-powered dams (NPDs) are dams that do not include hydraulic turbine (hydropower) equipment. Currently, there are more than 80,000 such dams in the United States, which provide a variety of non-energy benefits, including flood control, water supply, navigation, and recreation. Approximately 500 of these NPDs are identified as having the potential to add hydropower generation (totaling up to a capacity of more than 8200 MW). A large share of investment costs and environmental impacts of dam construction have already been incurred at these NPDs. Hence, adding power to the existing dam structure is hypothesized to be achieved at a lower cost, with less risk, and a shorter timeframe than the development required for new dam construction. The abundance of NPDs, the associated environmental favorability, and cost advantages, combined with the reliability, predictability, and dispatchability of hydropower, make NPDs a strong candidate in the nation’s renewable energy portfolio. To assess the NPD to hydropower conversion potential, in this study, we developed a GIS-based multi-criterial decision analysis tool, which allows users to rank these NPDs based on the grid, community, industry, and environmental impacts (i.e., GCIE impacts). This web-based interactive tool (developed using open-source Python and JavaScript) lets the user choose from a wide range of features to define each of the GCIE impact scores through a user-friendly graphical user interface. These features are related to dam operation, hydropower generation opportunity, power market economy, social vulnerability and risk, proximity to critical infrastructure and energy generating facilities, environmental concerns (air, water, and critical habitat), and exposure to natural hazards. The overall priority score of NPDs is calculated based on user-defined weights for each of the GCIE impact scores. Besides ranking NPDs, the tool can also be used to estimate the energy-storage feasibility (battery, hydrogen, and pump-storage hydropower) at each of the potential sites.

13 HYDRO ENERGY↗

Time-resolved spectra of dense plasma focus using spectrometer, streak camera, and CCD combination

A time-resolving spectrographic instrument has been assembled with the primary components of a spectrometer, image-converting streak camera, and CCD recording camera, for the primary purpose of diagnosing highly dynamic plasmas. A collection lens defines the sampled region and couples light from the plasma into a step index, multimode fiber which leads to the spectrometer. The output spectrum is focused onto the photocathode of the streak camera, the output of which is proximity-coupled to the CCD. The spectrometer configuration is essentially Czerny-Turner, but off-the-shelf Nikon refraction lenses, rather than mirrors, are used for practicality and flexibility. Only recently assembled, the instrument requires significant refinement, but has now taken data on both bridge wire and dense plasma focus experiments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Ultra-high speed photomultiplier tubes with nanosecond gating for fusion diagnostics

Fusion diagnostics can involve the measurement of ultra-fast optical pulses, often in close temporal proximity. We present a solution for the diagnostics of gamma reaction history and neutron time of flight by using microchannel plate based photomultiplier tubes (PMTs). The time response of the PMTs can be as fast as 100 ps FWHM and with a gain of up to 10{sup 7}. To observe small events in close temporal proximity to much larger signals such as the down-scattered fraction, the response of MCP-PMTs can be gated with an on/off ratio of up to 10{sup 13} in just 2 ns.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Tendency of a rotating electron plasma to approach the Brillouin limit

In this study, a neutral plasma is considered to be immersed in an axial magnetic field together with a radial electric field. If the electrons are magnetized, but the ions are not magnetized, then the electrons will rotate but the ions will not rotate, leading to current generation. The currents, in turn, weaken the axial magnetic field, leading to an increase in the rotation frequency of the slow Brillouin mode. This produces a positive feedback effect, further weakening the magnetic field. The operating point thus tends to drift towards the Brillouin limit, possibly finding stability only in proximity to the limit itself. An example of this effect might be the cylindrical Hall thruster configuration.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effect of dimensionality on vapor-liquid phase transition

Dimensionality play significant role on ‘phase transitions’. Fluids in macroscopic confinement (bulk or 3-Dimensional, 3D) do not show significant changes in their phase transition properties with extent of confinement, since the number of molecules away from the surrounding surfaces is astronomically higher than the number of molecules in close proximity of the confining surfaces. In microscopic confinement (quasi 3D to quasi-2D), however, the number of molecules away from the close proximity of the surface is not as high as is the case with macroscopic (3D) confinement. Hence, under the same thermodynamic conditions ‘phase transition’ properties at microscopic confinement may not remain the same as the macroscopic or 3D values. Phase transitions at extremely small scale become very sensitive to the dimensions as well as the surface characteristics of the system. In this work our investigations reveal the effect of dimensionality on the phase transition from 3D to quasi-2D to 2D behavior. We have used grand canonical transition matrix Monte Carlo simulation to understand the vapor–liquid phase transitions from 3D to quasi-2D behavior. Such studies can be helpful in understanding and controlling the fluid film behaviour confined between solid surfaces of few molecular diameters, for example, in lubrication applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved time response for large area microchannel plate photomultiplier tubes in fusion diagnostics

Fusion diagnostics that utilise high speed scintillators often need to capture a large area of light with a high degree of time accuracy. Microchannel plate (MCP) photomultiplier tubes (PMTs) are recognised as the leading device for capturing fast optical signals. However, when manufactured in their traditional proximity focused construction, the time response performance is reduced as the active area increases. This is due to two main factors: the capacitance of a large anode and the difficulty of obtaining small pore MCPs with a large area. Collaboration between Photek and AWE has produced prototype devices that combine the excellent time response of small area MCP-PMTs with a large active area by replacing the traditional proximity-gap front section with an electro-optically focused photocathode to MCP. We present results from both single and double MCP devices with a 40 mm diameter active area and show simulations for the 100 mm device being built this year.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Research Update: Spatially resolved mapping of electronic structure on atomic level by multivariate statistical analysis

Atomic level spatial variability of electronic structure in Fe-based superconductor FeTe0.55Se0.45 (Tc = 15 K) is explored using current-imaging tunneling-spectroscopy. Multivariate statistical analysis of the data differentiates regions of dissimilar electronic behavior that can be identified with the segregation of chalcogen atoms, as well as boundaries between terminations and near neighbor interactions. Subsequent clustering analysis allows identification of the spatial localization of these dissimilar regions. Similar statistical analysis of modeled calculated density of states of chemically inhomogeneous FeTe1 x Sex structures further confirms that the two types of chalcogens, i.e., Te and Se, can be identified by their electronic signature and differentiated by their local chemical environment. This approach allows detailed chemical discrimination of the scanning tunneling microscopy data including separation of atomic identities, proximity, and local configuration effects and can be universally applicable to chemically and electronically inhomogeneous surfaces.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗